EP3590907B1 - Dielectric composition and electronic component - Google Patents
Dielectric composition and electronic component Download PDFInfo
- Publication number
- EP3590907B1 EP3590907B1 EP18761436.7A EP18761436A EP3590907B1 EP 3590907 B1 EP3590907 B1 EP 3590907B1 EP 18761436 A EP18761436 A EP 18761436A EP 3590907 B1 EP3590907 B1 EP 3590907B1
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- EP
- European Patent Office
- Prior art keywords
- dielectric
- film
- substrate
- lower electrode
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 39
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 33
- 230000008021 deposition Effects 0.000 claims description 11
- 239000010408 film Substances 0.000 description 85
- 239000010409 thin film Substances 0.000 description 44
- 239000000758 substrate Substances 0.000 description 37
- 239000003990 capacitor Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 27
- 239000013078 crystal Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 238000009413 insulation Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 239000003989 dielectric material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910002976 CaZrO3 Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004549 pulsed laser deposition Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 229910014031 strontium zirconium oxide Inorganic materials 0.000 description 5
- 229910004205 SiNX Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000010295 mobile communication Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- -1 Al2Ox Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910003200 NdGaO3 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- H01G4/30—Stacked capacitors
- H01G4/306—Stacked capacitors made by thin film techniques
Definitions
- the present invention relates to a dielectric deposition film constituted by a dielectric composition and an electronic component having a dielectric film including the dielectric composition.
- the frequency bands being used is high frequency bands such as GHz.
- Some of high frequency components such as a filter or a combination of filters for example a duplexer, a diplexer, and the like which are used at high frequency bandwidth mentioned in above uses dielectric properties of the dielectric material. For such dielectric material, it is demanded to have a low dielectric loss and to pass a specific frequency selectively.
- the dielectric material applied to the high frequency electronic component at high frequency bands is demanded to have a low dielectric loss and a high relative permittivity at high frequency bands.
- a Q value is a reciprocal of the dielectric loss, in other words, the dielectric material having a high relative permittivity and a high Q value at high frequency band is demanded.
- amorphous SiN x film As a conventional dielectric material having a low dielectric loss at GHz bands, for example an amorphous SiN x film may be mentioned.
- a relative permittivity ( ⁇ r) of the amorphous SiN x film is 6.5 or so which is low and it was difficult to make the high frequency component more compact.
- Non-Patent Document 1 discloses that a CaZrO 3 amorphous thin film can be obtained by performing an annealing treatment to the CaZrO 3 thin film at a predetermined temperature. According to Non-Patent Document 1, this CaZrO 3 amorphous thin film has a relative permittivity of 12.8 to 16.0 at a measuring frequency of 100 kHz and a dielectric loss of 0.0018 to 0.0027 at a measuring frequency of 100 kHz.
- Non-Patent Document 2 discloses a SrZrO 3 thin film and this SrZrO 3 thin film has a relative permittivity of 24 to 27 within a measuring frequency of 2.6 to 11.2 MHz and a dielectric loss of 0.01 to 0.02 within a measuring frequency of 2.6 to 11.2 MHz.
- Non-Patent Document 1 when the dielectric loss of the CaZrO 3 amorphous thin film described in Non-Patent Document 1 is converted to a Q value, it is 370 to 555 at a measuring frequency of 100 kHz. Also, according to FIG.7 of Non-Patent Document 1, when the measuring frequency is 1 MHz, the dielectric loss is 0.005 or more, that is a Q value is 200 or less. Therefore, in case the measuring frequency is within GHz bands, a Q value is expected to decrease even more.
- Non-Patent Document 2 when the dielectric loss of the SrZrO 3 thin film shown in Non-Patent Document 2 is converted to a Q value, it is 100 or less within the range of a measuring frequency of 2.6 to 11.2 MHz. Therefore, when the measuring frequency is within GHz bands, a Q value is expected to decrease even more as similar to the case of Non-Patent Document 1.
- the present invention is attained in view of such circumstances, and the object is to provide the dielectric composition having a high relative permittivity and a high Q value even at high frequency bands and also to provide an electronic component having a dielectric film constituted from the dielectric composition.
- the dielectric deposition film of the present invention is constituted by a dielectric composition whereby [1] the 4dielectric composition includes a complex oxide expressed by a general formula (aCaO + bSrO)-ZrO 2 as a main component, in which "a" and "b" of the general formula satisfy a ⁇ 0, b ⁇ 0, and 1.55 ⁇ a + b ⁇ 4.00, wherein a relative permittivity at 2 GHz is 13.0 or more and a Q value is 500 or more.
- a general formula (aCaO + bSrO)-ZrO 2 as a main component
- the dielectric composition having a high relative permittivity and a high Q value even at high frequency bands can be provided and also the electronic component having a dielectric film constituted from the dielectric composition can be provided.
- a thin film capacitor 10 as an example of the electronic component according to the present embodiment has a constitution in which a substrate 1, a lower electrode 3, a dielectric film 5, and an upper electrode 4 are stacked in this order.
- the lower electrode 3, the dielectric film 5, and the upper electrode 4 form a capacitor part and when the lower electrode 3 and the upper electrode 4 are connected to an external circuit and voltage is applied, the dielectric film 5 exhibits a predetermined capacitance, thereby the capacitor part function as a capacitor.
- an underlayer 2 is formed between the substrate 1 and the lower electrode 3 in order to improve adhesiveness between the substrate 1 and the lower electrode 3.
- a material constituting the underlayer 2 is not particularly limited as long as the adhesiveness between the substrate 1 and the lower electrode 3 can be sufficiently secured.
- the underlayer 2 when the lower electrode 3 is constituted from Cu, the underlayer 2 can be constituted from Cr; and when the lower electrode 3 is constituted from Pt, the underlayer 2 can be constituted from Ti.
- a protective film may be formed for blocking the dielectric film 5 from external atmosphere.
- a shape of a thin film capacitor is not particularly limited, and usually it is rectangular parallelepiped shape. Also, a size of the thin film capacitor is not particularly limited, and a thickness and a length may be determined appropriately depending on the purpose of use.
- the dielectric film 5 according to the invention is constituted from the dielectric composition according to the present embodiment described in below. Also, in the present embodiment, the dielectric film 5 is not constituted from a sintered body obtained by sintering a molded article of a raw material powder of the dielectric composition but preferably the dielectric film 5 is a dielectric deposition film of a thin film made by a known film forming method. Note that, the dielectric film 5 may be crystalline or amorphous; and in the present embodiment the dielectric film 5 is preferably crystalline.
- the thin film capacitor having such dielectric film 5 exhibits a high Q value of 500 or more and a high relative permittivity of 13.0 or more at 2 GHz.
- the thickness of the dielectric layer 5 is preferably 10 nm to 2000 nm, and more preferably 50 nm to 1000 nm.
- an insulation breakdown of the dielectric film 5 tends to easily occur. If the insulation breakdown occurs, a capacitor cannot exhibit its function.
- the dielectric film 5 is too thick, a larger electrode area is needed to attain larger capacitance of the capacitor, thus in some case it becomes difficult to make the electronic component more compact depending on the design of the electronic component.
- the dielectric film constituted from the dielectric composition according to the present embodiment can attain a high Q value even when the dielectric film is extremely thin.
- the thin film capacitor including the dielectric film 5 is processed using FIB (Focused Ion Beam) processing device and the obtained cross section is observed using SIM (Scanning Ion Microscope) and the like, thereby the thickness of the dielectric film 5 can be measured.
- FIB Fluorous Ion Beam
- SIM Sccanning Ion Microscope
- the dielectric composition of the film according to the invention includes an oxide expressed by a general formula (aCaO + bSrO)-ZrO 2 as a main component. That is, a complex oxide includes Ca and/or Sr and also includes Zr.
- a represents a content of CaO in terms of molar ratio with respect to a content of ZrO 2
- "b” represents a content of SrO in terms of molar ratio with respect to a content of ZrO 2 .
- "a" and "b” satisfy a ⁇ 0, b ⁇ 0, and 1.55 ⁇ a + b ⁇ 4.00.
- the above complex oxide is a complex oxide formed of oxide of divalent element and ZrO 2 .
- CaO and SrO are selected from alkaline earth metal oxides as the oxide of divalent element; and a total content of these are 1.55 times or more and 4.00 times or less in terms of molar ratio with respect to the content of ZrO 2 .
- the above mentioned complex oxide may be aCaO-ZrO 2 or bSrO-ZrO 2 . From the point of the dielectric properties, bSrO-ZrO 2 is preferable than aCaO-ZrO 2 ; and from the point of stability against water, aCaO-ZrO 2 is preferable than bSrO-ZrO 2 .
- a + b preferably satisfies preferably satisfies 1.55 ⁇ a+ b ⁇ 2.20.
- a + b satisfies 3.00 ⁇ a + b ⁇ 4.00.
- a + b satisfies 2.20 ⁇ a + b ⁇ 3.00.
- a high relative permittivity for example 15.0 or more
- a high Q value for example 550 or more
- the dielectric composition according to the present embodiment may include a trace amount of impurities, subcomponents, and the like as long as the present invention can exhibit its effect.
- the main component is 70 mol% or more and 100 mol% or less with respect to the entire dielectric composition.
- the substrate shown in FIG.1 is not particularly limited as long as it is constituted from a material having mechanical strength which can support the underlayer 2, the lower electrode 3, the dielectric film 5, and the upper electrode 4 which are formed on the substrate 1,.
- a single crystal substrate constituted from Si single crystal, SiGe single crystal, GaAs single crystal, InP single crystal, SrTiO 3 single crystal, MgO single crystal, LaAlO 3 single crystal, ZrO 2 single crystal, MgAl 2 O 4 single crystal, NdGaO 3 single crystal, and the like; a ceramic polycrystal substrate constituted from Al 2 O 3 polycrystal, ZnO polycrystal, SiO 2 polycrystal, and the like; a metal substrate constituted from metals such as Ni, Cu, Ti, W, Mo, Al, Pt, an alloy of these; and like may be mentioned.
- Si single crystal is used as the substrate.
- a thickness of the substrate 1 is for example between 10 ⁇ m to 5000 ⁇ m. When it is too thin, a mechanical strength may not be enough in some case, and when it is too thick, in some case the electronic component cannot be made compact.
- the above mentioned substrate 1 has a different resistivity depending on the material of the substrate.
- the substrate is constituted by the material having a low resistivity, current may leak towards the substrate side while the thin film capacitor is running, and this may affect the electric properties of the thin film capacitor.
- an insulation treatment is performed to the surface of the substrate 1 so that current does not leak towards the substrate 1 side while the capacitor is running.
- an insulation layer is preferably formed on the surface of the substrate 1.
- the material constituting the insulation layer and the thickness of the insulation layer are not particularly limited.
- the material constituting the insulation layer SiO 2 , Al 2 O 3 , Si 3 N x , and the like may be mentioned as examples.
- the thickness of the insulation layer is preferably 0.01 ⁇ m or more.
- the lower electrode 3 is formed in a thin film form on the substrate 1 via the underlayer 2.
- the dielectric film 5 is placed between the lower electrode 3 and the upper electrode 4 which is described in below and the lower electrode 3 is an electrode which allows the dielectric film 5 to function as a capacitor.
- the material constituting the lower electrode 3 is not particularly limited as long as it has conductivity.
- metals such as Pt, Ru, Rh, Pd, Ir, Au, Ag, Cu, Ni, and the like; the alloy thereof; or a conductive oxide; and the like may be mentioned.
- a thickness of the lower electrode 3 is not particularly limited as long as the lower electrode 3 functions as an electrode.
- the thickness is preferably 0.01 ⁇ m or more.
- the upper electrode 4 is formed in a thin film form on the surface of the dielectric film 5.
- the dielectric film 5 is placed between the upper electrode 4 and the lower electrode 3 and the upper electrode 4 is an electrode which allows the dielectric film 5 to function as a capacitor. Therefore, the upper electrode 4 and the lower electrode 3 have a different polarity.
- a material constituting the upper electrode 4 is not particularly limited as long as it has conductivity.
- metals such as Pt, Ru, Rh, Pd, Ir, Au, Ag, Cu, Ni, and the like; the alloy thereof; or a conductive oxide; and the like may be mentioned.
- the substrate 1 is prepared.
- the substrate 1 for example when using a Si single crystal substrate, an insulation layer is formed on one of a main face of the substrate.
- a method for forming the insulation layer a known method for forming a film such as a thermal oxidation method, a CVD (Chemical Vapor Deposition) method, and the like may be used.
- a thin film made of a material constituting an underlayer is formed on the insulation layer which has been formed using a known method for forming a film thereby the underlayer 2 is formed.
- a thin film made of a material constituting a lower electrode is formed on the underlayer 2 using a known method for forming a film thereby the lower electrode 3 is formed.
- a heat treatment may be carried out in order to improve adhesiveness between the underlayer 2 and the lower electrode 3 and also to improve a stability of the lower electrode 3.
- a heat treatment condition for example a temperature rising rate is preferably 10°C/min to 2000°C/min and more preferably 100°C/min to 1000°C/min.
- a holding temperature during the heat treatment is preferably 400°C to 800°C and a holding time is preferably 0.1 hour to 4.0 hours.
- the dielectric film 5 is formed on the lower electrode 3.
- the dielectric film 5 is formed as a deposition film of which the material constituting the dielectric film 5 is deposited in a film form on the lower electrode 3 by a known method for forming a film.
- a vacuum deposition method for example a vacuum deposition method, a sputtering method, a PLD method (Pulsed Laser Deposition method), a MO-CVD method (Metal Organic Chemical Vapor Deposition method), a MOD method (Metal Organic Decomposition method), a sol-gel method, a CSD method (Chemical Solution Deposition method), and the like may be mentioned.
- a trace amount of impurities, subcomponents, and the like may be included in a used raw material (a deposition material, various target materials, an organometallic material, and the like) when the film is formed but as long as the desired dielectric properties can be attained this may not be an issue.
- a thin film of material constituting the upper electrode is formed by a known method for forming a film on the dielectric film 5 which has been formed; thereby the upper electrode 4 is formed.
- the thin film capacitor 10 having a capacitor part (the lower electrode 3, the dielectric film 5, and the upper electrode 4) on the substrate 1 as shown in FIG. 1 can be obtained.
- a protective film for protecting the dielectric film 5 may be formed so as to cover at least part of the dielectric film 5 which is exposed to outside using a known method for forming a film.
- the present embodiment focuses on the complex oxide of ZrO 2 and the oxide of divalent element as the dielectric composition having good dielectric properties at high frequency bands. Further, as the divalent element, Ca and Sr are only selected, and also a total molar amount of these oxides with respect to ZrO 2 is controlled to be in the specific range larger than 1. That is, an excess amount of CaO and/or SrO are included with respect to ZrO 2 .
- a high relative permittivity for example 13.0 or more
- a high Q value for example 500 or more
- high frequency bands for example 2 GHz. That is, when a Q value is converted to a dielectric loss, it is 0.002 or less which means that extremely low dielectric loss is attained even at frequency of GHz bands.
- a dielectric composition focused on obtaining a high relative permittivity a dielectric composition focused on obtaining a high Q value
- a dielectric composition focused on balancing a relative permittivity and a Q value can be obtained depending on the purpose of use.
- the dielectric composition according to the present embodiment can attain both a high relative permittivity and a high Q value at high frequency bands, thus the electronic component using the dielectric composition according to the present embodiment can be compact compared to a conventional electronic component, and also the electronic component of the present embodiment can selectively pass a specific frequency compared to a conventional electronic component at high frequency bands.
- the dielectric film is constituted only by the dielectric composition of the present invention but the dielectric film may be a multilayer structure combined with a film of other dielectric composition.
- the dielectric film may be a multilayer structure combined with a film of other dielectric composition.
- an amorphous dielectric film or crystal film of known Si 3 N x , SiO x , Al 2 O x , ZrO x , Ta 2 O x , and the like changes in impedance and relative permittivity of the dielectric film 5 caused by a temperature change can be regulated.
- the underlayer is formed to improve the adhesiveness between the substrate and the lower electrode, however when the adhesiveness between the substrate and the lower electrode can be secured sufficiently, and then the underlayer may be omitted. Also, when metals such as Cu, Ni, Pt, and the like; an alloy thereof; a conductive oxide; and the like which can be used as an electrode is used as the material constituting the substrate, then the underlayer and the lower electrode can be omitted.
- powders of CaCO 3 , SrCO 3 , and ZrO 2 were prepared as raw material powders for producing a target. These powders were weighed so as to satisfy compositions of Sample No.1 to Sample No.24 shown in Table 1.
- the weighed raw material powders, absolute ethanol, and ZrO 2 beads having ⁇ 2 mm were put in a wide mouth polypropylene pot having a capacity of 1 L and wet mixing was carried out for 20 hours. Then, a mixed powder slurry was dried for 20 hours at 100°C, and the obtained mixed powder was put in Al 2 O 3 crucible, then it was calcined for 5 hours at 1250°C in air atmosphere; thereby a calcined powder was obtained.
- the obtained calcined powder was molded using a uniaxial pressing machine thereby a molded article was obtained.
- the molding condition was pressure of 2.0 ⁇ 10 8 Pa at room temperature.
- the obtained molded article was fired in a temperature rising rate of 200°C/hour at a holding temperature of 1600°C to 1700°C for a holding time of 12 hours in air atmosphere; thereby a sintered body was obtained.
- Both surfaces of the obtained sintered body were polished using a cylindrical grinder so that the thickness of the obtained sintered body was 4 mm, thereby the target for forming the dielectric film was obtained.
- a square substrate of 10 mm x 10 mm having a SiO 2 insulation layer with a thickness of 6 ⁇ m on a surface of the Si single crystal substrate with a thickness of 350 ⁇ m was prepared.
- a Ti thin film having a thickness of 20 nm as an underlayer was formed by a sputtering method.
- a Pt thin film as the lower electrode having a thickness of 100 nm was formed by a sputtering method.
- a heat treatment was performed in a temperature rising rate of 400°C/min at a holding temperature of 700°C for a temperature holding time of 0.5 hour under oxygen atmosphere.
- a dielectric film was formed on the Ti/Pt thin film after the heat treatment.
- the dielectric film was formed by a PLD method so that the thickness was 400 nm on the lower electrode using the target formed in above.
- a condition for forming the film by a PLD method was oxygen pressure of 1.0 ⁇ 10 -1 Pa and the substrate was heated to 200°C. Also, in order to expose part of the lower electrode, a metal mask was used to form an area where the dielectric film was not formed.
- an Ag thin film as an upper electrode was formed on the obtained dielectric film using a deposition machine.
- the upper electrode is formed so as to have a shape having a diameter of 100 ⁇ m and a thickness of 100 nm using the metal mask.
- a composition of the dielectric film was analyzed using XRF (X-ray fluorescence element analysis) for all of the samples to confirm that the composition matched the composition shown in Table 1. Also, the thin film capacitor was processed using FIB and the obtained cross section was observed using SIM to measure the length, thereby the thickness of the dielectric film was obtained.
- XRF X-ray fluorescence element analysis
- a relative permittivity and a Q value were calculated (no unit) from the thickness of the above obtained dielectric film and a capacitance which was measured using an RF impedance/material analyzer (4991A made by Agilent) at a standard temperature of 25°C by inputting a frequency of 2 GHz, an input signal level (measuring voltage) of 0.5 Vrms.
- a relative permittivity of 13.0 or more was considered good which is about 2 times of the relative permittivity of amorphous SiN x film.
- a Q value of 500 or more was considered good since a Q value of an amorphous SiN x film was about 500. Results are shown in Table 1, FIG.2A, and FIG.2B .
- the thin film capacitor was produced by the same method as Sample No.1 of Example 1 except for forming the dielectric film by a sputtering method, and the same evaluations as Example 1 were carried out.
- As a target the same target as the PLD target of Example 1 was used. Results are shown in Table 2.
- the thin film capacitor was produced by the same method as Sample No.1 of Example 1 except for changing the thickness of the dielectric film, and the same evaluations as Example 1 were carried out. Results are shown in Table 2.
- Table 2 Sam ple No. (aCa0+ bSr0)-Zr0 2 Properties a b a+b Th ickness (nm) 0 at2GHz (-) Relative perm ittiv ity at2GHz (-)
- Example 1 1 1.51 0.00 1.51 400 502 19.8
- Example 2 25 1.51 0.00 1.51 400 514 19.7
- Example 3 26 1.51 0.00 1.51 200 505 19.7 27 1.51 0.00 1.51 800 518 19.8
- An electronic component having a dielectric film including a dielectric composition according to the present invention can attain both a high relative permittivity (for example 13.0 or more) and a high Q value (for example 500 or more) even at high frequency bands. Therefore, such electronic component can be suitably used as a high frequency component.
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Description
- The present invention relates to a dielectric deposition film constituted by a dielectric composition and an electronic component having a dielectric film including the dielectric composition.
- Mobile communication devices such as smart phones and the like are demanded to attain high performance, and for example in order to achieve a high speed and a high capacity communication, a number of frequency bands being used is increasing. The frequency bands being used is high frequency bands such as GHz. Some of high frequency components such as a filter or a combination of filters for example a duplexer, a diplexer, and the like which are used at high frequency bandwidth mentioned in above uses dielectric properties of the dielectric material. For such dielectric material, it is demanded to have a low dielectric loss and to pass a specific frequency selectively.
- Also, as the mobile communication devices attained a higher performance, a number of electronic components mounted to one mobile communication device are increasing. Therefore, in order to maintain the size of the mobile communication device, it is also demanded to make the electronic component more compact. In order to make the high frequency component using the dielectric material more compact, it is necessary to reduce an area of electrode, thus a high relative permittivity of the dielectric material is demanded in order to compensate a capacitance decrease.
- Therefore, the dielectric material applied to the high frequency electronic component at high frequency bands is demanded to have a low dielectric loss and a high relative permittivity at high frequency bands. A Q value is a reciprocal of the dielectric loss, in other words, the dielectric material having a high relative permittivity and a high Q value at high frequency band is demanded.
- As a conventional dielectric material having a low dielectric loss at GHz bands, for example an amorphous SiNx film may be mentioned. However, a relative permittivity (εr) of the amorphous SiNx film is 6.5 or so which is low and it was difficult to make the high frequency component more compact.
- However, Non-Patent
Document 1 discloses that a CaZrO3 amorphous thin film can be obtained by performing an annealing treatment to the CaZrO3 thin film at a predetermined temperature. According to Non-PatentDocument 1, this CaZrO3 amorphous thin film has a relative permittivity of 12.8 to 16.0 at a measuring frequency of 100 kHz and a dielectric loss of 0.0018 to 0.0027 at a measuring frequency of 100 kHz. - Also, Non-Patent
Document 2 discloses a SrZrO3 thin film and this SrZrO3 thin film has a relative permittivity of 24 to 27 within a measuring frequency of 2.6 to 11.2 MHz and a dielectric loss of 0.01 to 0.02 within a measuring frequency of 2.6 to 11.2 MHz. -
- Non-Patent Document 1: T. Yu, et al, "Preparation and characterization of sol-gel derived CaZrO3 dielectric thin films for high-k applications", Physica B, 348 (2004) 440-445
- Non-Patent Document 2: X. B. Lu, et al, "Dielectric properties of SrZrO3 thin films prepared by pulsed laser deposition", Applied Physics A, 77, 481-484(2003). Documents
EP2924693A2 andUS2014/0378295A1 describe dielectric films comprising Ca, Sr and Zr. - However, when the dielectric loss of the CaZrO3 amorphous thin film described in
Non-Patent Document 1 is converted to a Q value, it is 370 to 555 at a measuring frequency of 100 kHz. Also, according to FIG.7 of Non-PatentDocument 1, when the measuring frequency is 1 MHz, the dielectric loss is 0.005 or more, that is a Q value is 200 or less. Therefore, in case the measuring frequency is within GHz bands, a Q value is expected to decrease even more. - Also, when the dielectric loss of the SrZrO3 thin film shown in Non-Patent
Document 2 is converted to a Q value, it is 100 or less within the range of a measuring frequency of 2.6 to 11.2 MHz. Therefore, when the measuring frequency is within GHz bands, a Q value is expected to decrease even more as similar to the case ofNon-Patent Document 1. - The present invention is attained in view of such circumstances, and the object is to provide the dielectric composition having a high relative permittivity and a high Q value even at high frequency bands and also to provide an electronic component having a dielectric film constituted from the dielectric composition.
- In order to attain the above object, the dielectric deposition film of the present invention is constituted by a dielectric composition whereby [1] the 4dielectric composition includes a complex oxide expressed by a general formula (aCaO + bSrO)-ZrO2 as a main component, in which "a" and "b" of the general formula satisfy a ≥ 0, b ≥ 0, and 1.55 ≤ a + b ≤ 4.00, wherein a relative permittivity at 2 GHz is 13.0 or more and a Q value is 500 or more.
-
- [2] The dielectric composition according to [1], wherein "a" and "b" of the general formula satisfy 1.55 ≤ a + b ≤ 2.20.
- [3] The dielectric composition according to [1], wherein "a" and "b" of the general formula satisfy 3.00 ≤ a + b ≤ 4.00.
- [4] An electronic component comprising a dielectric film including the dielectric composition according to any one of [1] to [3].
- According to the present invention, the dielectric composition having a high relative permittivity and a high Q value even at high frequency bands can be provided and also the electronic component having a dielectric film constituted from the dielectric composition can be provided.
-
-
FIG.1 is a cross section of a thin film capacitor as an electronic component according to one embodiment of the present invention. -
FIG.2A is a graph showing a relation between "a + b" and Q value at 2 GHz of examples and comparative examples of the present invention. -
FIG.2B is a graph showing a relation between "a + b" and a relative permittivity at 2 GHz of examples and comparative examples of the present invention. - Hereinafter, the present invention is described in detail in below listed order based on a specific embodiment.
- 1. Thin Film Capacitor
- 1.1 Overall Constitution of Thin Film Capacitor
- 1.2 Dielectric Film
1.2.1 Dielectric Composition - 1.3 Substrate
- 1.4 Lower Electrode
- 1.5 Upper Electrode
- 2. Method in Producing Thin Film Capacitor
- 3. Effects of the Present Embodiment
- 4. Modified Example
- First, as an electronic component according to the present embodiment, a thin film capacitor in which a dielectric layer is constituted from a thin dielectric film is explained.
- As shown in
FIG.1 , athin film capacitor 10 as an example of the electronic component according to the present embodiment has a constitution in which asubstrate 1, alower electrode 3, adielectric film 5, and anupper electrode 4 are stacked in this order. Thelower electrode 3, thedielectric film 5, and theupper electrode 4 form a capacitor part and when thelower electrode 3 and theupper electrode 4 are connected to an external circuit and voltage is applied, thedielectric film 5 exhibits a predetermined capacitance, thereby the capacitor part function as a capacitor. Each constitution element will be discussed in detail in below. - Also, in the present embodiment, an
underlayer 2 is formed between thesubstrate 1 and thelower electrode 3 in order to improve adhesiveness between thesubstrate 1 and thelower electrode 3. A material constituting theunderlayer 2 is not particularly limited as long as the adhesiveness between thesubstrate 1 and thelower electrode 3 can be sufficiently secured. For example, when thelower electrode 3 is constituted from Cu, theunderlayer 2 can be constituted from Cr; and when thelower electrode 3 is constituted from Pt, theunderlayer 2 can be constituted from Ti. - Also, in the
thin film capacitor 10 shown inFIG.1 , a protective film may be formed for blocking thedielectric film 5 from external atmosphere. - Note that, a shape of a thin film capacitor is not particularly limited, and usually it is rectangular parallelepiped shape. Also, a size of the thin film capacitor is not particularly limited, and a thickness and a length may be determined appropriately depending on the purpose of use.
- The
dielectric film 5 according to the invention is constituted from the dielectric composition according to the present embodiment described in below. Also, in the present embodiment, thedielectric film 5 is not constituted from a sintered body obtained by sintering a molded article of a raw material powder of the dielectric composition but preferably thedielectric film 5 is a dielectric deposition film of a thin film made by a known film forming method. Note that, thedielectric film 5 may be crystalline or amorphous; and in the present embodiment thedielectric film 5 is preferably crystalline. - The thin film capacitor having such
dielectric film 5 exhibits a high Q value of 500 or more and a high relative permittivity of 13.0 or more at 2 GHz. - The thickness of the
dielectric layer 5 is preferably 10 nm to 2000 nm, and more preferably 50 nm to 1000 nm. When thedielectric film 5 is too thin, an insulation breakdown of thedielectric film 5 tends to easily occur. If the insulation breakdown occurs, a capacitor cannot exhibit its function. On the other hand, when thedielectric film 5 is too thick, a larger electrode area is needed to attain larger capacitance of the capacitor, thus in some case it becomes difficult to make the electronic component more compact depending on the design of the electronic component. - Usually, Q value tends to decrease when a dielectric becomes thinner, and it is necessary to constitute a dielectric to have certain degree of thickness in order to attain a high Q value. However, the dielectric film constituted from the dielectric composition according to the present embodiment can attain a high Q value even when the dielectric film is extremely thin.
- Note that, the thin film capacitor including the
dielectric film 5 is processed using FIB (Focused Ion Beam) processing device and the obtained cross section is observed using SIM (Scanning Ion Microscope) and the like, thereby the thickness of thedielectric film 5 can be measured. - The dielectric composition of the film according to the invention includes an oxide expressed by a general formula (aCaO + bSrO)-ZrO2 as a main component. That is, a complex oxide includes Ca and/or Sr and also includes Zr. In the above general formula, "a" represents a content of CaO in terms of molar ratio with respect to a content of ZrO2, and "b" represents a content of SrO in terms of molar ratio with respect to a content of ZrO2. In the present embodiment, "a" and "b" satisfy a ≥ 0, b ≥ 0, and 1.55 ≤ a + b ≤ 4.00.
- Also, as it is apparent from the above mentioned general formula, the above complex oxide is a complex oxide formed of oxide of divalent element and ZrO2. In the present embodiment, CaO and SrO are selected from alkaline earth metal oxides as the oxide of divalent element; and a total content of these are 1.55 times or more and 4.00 times or less in terms of molar ratio with respect to the content of ZrO2. By having "a" and "b" within the above range, excellent dielectric properties (high Q value and high relative permittivity at high frequency bands) can be attained.
- When "a + b" is too small, for example when of a + b = 1.00, it tends to be difficult to attain a high Q value at high frequency bands. When "a + b" is too large, it tends to be difficult to attain a high relative permittivity at high frequency bands.
- Note that, when of a + b= 1.00, the complex oxide is shown as (Ca, Sr)ZrOs. When a = 1.00, the complex oxide is represented as CaZrO3; and when b = 1.00, then the complex oxide is represented as SrZrO3. Therefore, from the point of (Ca, Sr)ZrOs, the above complex oxide has a constitution which includes an excessive amount of oxide of divalent element (divalent element oxide rich composition) with respect to the content of ZrO2.
- Conventionally, the above mentioned CaO and/or SrO rich composition was rarely considered for use because the excess amount of CaO and/or SrO easily reacts with water.
- Also, as long as 1.55 ≤ a + b ≤ 4.00 is satisfied, either "a" or "b" may be zero. Therefore, the above mentioned complex oxide may be aCaO-ZrO2 or bSrO-ZrO2. From the point of the dielectric properties, bSrO-ZrO2 is preferable than aCaO-ZrO2; and from the point of stability against water, aCaO-ZrO2 is preferable than bSrO-ZrO2.
- In the present embodiment, "a + b" preferably satisfies preferably satisfies 1.55 ≤ a+ b ≤ 2.20. By having "a + b" within the above range, even higher relative permittivity (for example 18.0 or more) can be attained while attaining a high Q value (for example 500 or more) at high frequency bands (for example 2 GHz).
- Also, preferably "a + b" satisfies 3.00 ≤ a + b ≤ 4.00. By having "a + b" within the above range, even higher Q value (for example 570 or more) can be attained while attaining a high relative permittivity (for example 13.0 or more) at high frequency bands (for example 2 GHz).
- Also, preferably "a + b" satisfies 2.20 < a + b < 3.00. By having "a + b" within the above range, a high relative permittivity (for example 15.0 or more) and a high Q value (for example 550 or more) can be both attained at high frequency bands (for example 2 GHz).
- Also, the dielectric composition according to the present embodiment may include a trace amount of impurities, subcomponents, and the like as long as the present invention can exhibit its effect. In the present embodiment, the main component is 70 mol% or more and 100 mol% or less with respect to the entire dielectric composition.
- The substrate shown in
FIG.1 is not particularly limited as long as it is constituted from a material having mechanical strength which can support theunderlayer 2, thelower electrode 3, thedielectric film 5, and theupper electrode 4 which are formed on thesubstrate 1,. For example, a single crystal substrate constituted from Si single crystal, SiGe single crystal, GaAs single crystal, InP single crystal, SrTiO3 single crystal, MgO single crystal, LaAlO3 single crystal, ZrO2 single crystal, MgAl2O4 single crystal, NdGaO3 single crystal, and the like; a ceramic polycrystal substrate constituted from Al2O3 polycrystal, ZnO polycrystal, SiO2 polycrystal, and the like; a metal substrate constituted from metals such as Ni, Cu, Ti, W, Mo, Al, Pt, an alloy of these; and like may be mentioned. In the present embodiment, from the point of low cost and processability, Si single crystal is used as the substrate. - A thickness of the
substrate 1 is for example between 10 µm to 5000 µm. When it is too thin, a mechanical strength may not be enough in some case, and when it is too thick, in some case the electronic component cannot be made compact. - The above mentioned
substrate 1 has a different resistivity depending on the material of the substrate. When the substrate is constituted by the material having a low resistivity, current may leak towards the substrate side while the thin film capacitor is running, and this may affect the electric properties of the thin film capacitor. Thus, when the resistivity of thesubstrate 1 is low, preferably an insulation treatment is performed to the surface of thesubstrate 1 so that current does not leak towards thesubstrate 1 side while the capacitor is running. - For example, when Si single crystal is used as the
substrate 1, an insulation layer is preferably formed on the surface of thesubstrate 1. As long as thesubstrate 1 and the capacitor part are sufficiently insulated, the material constituting the insulation layer and the thickness of the insulation layer are not particularly limited. In the present embodiment, as the material constituting the insulation layer, SiO2, Al2O3, Si3Nx, and the like may be mentioned as examples. Also, the thickness of the insulation layer is preferably 0.01 µm or more. - As shown in
FIG.1 , thelower electrode 3 is formed in a thin film form on thesubstrate 1 via theunderlayer 2. Thedielectric film 5 is placed between thelower electrode 3 and theupper electrode 4 which is described in below and thelower electrode 3 is an electrode which allows thedielectric film 5 to function as a capacitor. The material constituting thelower electrode 3 is not particularly limited as long as it has conductivity. For example, metals such as Pt, Ru, Rh, Pd, Ir, Au, Ag, Cu, Ni, and the like; the alloy thereof; or a conductive oxide; and the like may be mentioned. - A thickness of the
lower electrode 3 is not particularly limited as long as thelower electrode 3 functions as an electrode. In the present embodiment, the thickness is preferably 0.01 µm or more. - As shown in
FIG.1 , theupper electrode 4 is formed in a thin film form on the surface of thedielectric film 5. Thedielectric film 5 is placed between theupper electrode 4 and thelower electrode 3 and theupper electrode 4 is an electrode which allows thedielectric film 5 to function as a capacitor. Therefore, theupper electrode 4 and thelower electrode 3 have a different polarity. - As similar to the
lower electrode 3, a material constituting theupper electrode 4 is not particularly limited as long as it has conductivity. For example, metals such as Pt, Ru, Rh, Pd, Ir, Au, Ag, Cu, Ni, and the like; the alloy thereof; or a conductive oxide; and the like may be mentioned. - Next, an example of the method for producing the
thin film capacitor 10 shown inFIG.1 is described in below. - First, the
substrate 1 is prepared. As thesubstrate 1, for example when using a Si single crystal substrate, an insulation layer is formed on one of a main face of the substrate. As a method for forming the insulation layer, a known method for forming a film such as a thermal oxidation method, a CVD (Chemical Vapor Deposition) method, and the like may be used. - Next, a thin film made of a material constituting an underlayer is formed on the insulation layer which has been formed using a known method for forming a film thereby the
underlayer 2 is formed. - After the
underlayer 2 is formed, a thin film made of a material constituting a lower electrode is formed on theunderlayer 2 using a known method for forming a film thereby thelower electrode 3 is formed. - After the
lower electrode 3 is formed, a heat treatment may be carried out in order to improve adhesiveness between theunderlayer 2 and thelower electrode 3 and also to improve a stability of thelower electrode 3. As a heat treatment condition, for example a temperature rising rate is preferably 10°C/min to 2000°C/min and more preferably 100°C/min to 1000°C/min. A holding temperature during the heat treatment is preferably 400°C to 800°C and a holding time is preferably 0.1 hour to 4.0 hours. When the heat treatment condition is out of the above mentioned range, theunderlayer 2 and thelower electrode 3 may not adhere sufficiently and also the surface of thelower electrode 3 easily becomes rough. As a result, the dielectric properties of thedielectric film 5 tend to easily decrease. - Next, the
dielectric film 5 is formed on thelower electrode 3. In the present embodiment, thedielectric film 5 is formed as a deposition film of which the material constituting thedielectric film 5 is deposited in a film form on thelower electrode 3 by a known method for forming a film. - As a known method for forming a film, for example a vacuum deposition method, a sputtering method, a PLD method (Pulsed Laser Deposition method), a MO-CVD method (Metal Organic Chemical Vapor Deposition method), a MOD method (Metal Organic Decomposition method), a sol-gel method, a CSD method (Chemical Solution Deposition method), and the like may be mentioned. Note that, a trace amount of impurities, subcomponents, and the like may be included in a used raw material (a deposition material, various target materials, an organometallic material, and the like) when the film is formed but as long as the desired dielectric properties can be attained this may not be an issue.
- Next, a thin film of material constituting the upper electrode is formed by a known method for forming a film on the
dielectric film 5 which has been formed; thereby theupper electrode 4 is formed. - By going through the above mentioned steps, the
thin film capacitor 10 having a capacitor part (thelower electrode 3, thedielectric film 5, and the upper electrode 4) on thesubstrate 1 as shown inFIG. 1 can be obtained. Note that, a protective film for protecting thedielectric film 5 may be formed so as to cover at least part of thedielectric film 5 which is exposed to outside using a known method for forming a film. - The present embodiment focuses on the complex oxide of ZrO2 and the oxide of divalent element as the dielectric composition having good dielectric properties at high frequency bands. Further, as the divalent element, Ca and Sr are only selected, and also a total molar amount of these oxides with respect to ZrO2 is controlled to be in the specific range larger than 1. That is, an excess amount of CaO and/or SrO are included with respect to ZrO2.
- By doing so, when the dielectric composition according to the present embodiment is deposited as a thin deposition film, a high relative permittivity (for example 13.0 or more) and a high Q value (for example 500 or more) can be attained at high frequency bands (for example 2 GHz). That is, when a Q value is converted to a dielectric loss, it is 0.002 or less which means that extremely low dielectric loss is attained even at frequency of GHz bands.
- Also, by changing the range of "a + b", a dielectric composition focused on obtaining a high relative permittivity, a dielectric composition focused on obtaining a high Q value, and a dielectric composition focused on balancing a relative permittivity and a Q value can be obtained depending on the purpose of use.
- The dielectric composition according to the present embodiment can attain both a high relative permittivity and a high Q value at high frequency bands, thus the electronic component using the dielectric composition according to the present embodiment can be compact compared to a conventional electronic component, and also the electronic component of the present embodiment can selectively pass a specific frequency compared to a conventional electronic component at high frequency bands.
- The above embodiment was described based on the case in which the dielectric film is constituted only by the dielectric composition of the present invention but the dielectric film may be a multilayer structure combined with a film of other dielectric composition. For example, by forming a multilayer structure with an amorphous dielectric film or crystal film of known Si3Nx, SiOx, Al2Ox, ZrOx, Ta2Ox, and the like, changes in impedance and relative permittivity of the
dielectric film 5 caused by a temperature change can be regulated. - In the above embodiment, the underlayer is formed to improve the adhesiveness between the substrate and the lower electrode, however when the adhesiveness between the substrate and the lower electrode can be secured sufficiently, and then the underlayer may be omitted. Also, when metals such as Cu, Ni, Pt, and the like; an alloy thereof; a conductive oxide; and the like which can be used as an electrode is used as the material constituting the substrate, then the underlayer and the lower electrode can be omitted.
- Hereinabove, the embodiment of the present invention has been described, but the present invention is not to be limited thereto and various modifications may be performed within the scope of the present invention.
- Hereinafter, the present invention is described in further detail using examples and comparative examples. Note that, the present invention is not to be limited below examples. Samples 1-3 and 25-27 are outside the invention as defined in the claims.
- First, a target necessary for forming a dielectric film was produced as described in below.
- As raw material powders for producing a target, powders of CaCO3, SrCO3, and ZrO2 were prepared. These powders were weighed so as to satisfy compositions of Sample No.1 to Sample No.24 shown in Table 1. The weighed raw material powders, absolute ethanol, and ZrO2 beads having φ2 mm were put in a wide mouth polypropylene pot having a capacity of 1 L and wet mixing was carried out for 20 hours. Then, a mixed powder slurry was dried for 20 hours at 100°C, and the obtained mixed powder was put in Al2O3 crucible, then it was calcined for 5 hours at 1250°C in air atmosphere; thereby a calcined powder was obtained.
- The obtained calcined powder was molded using a uniaxial pressing machine thereby a molded article was obtained. The molding condition was pressure of 2.0 × 108 Pa at room temperature.
- Then, the obtained molded article was fired in a temperature rising rate of 200°C/hour at a holding temperature of 1600°C to 1700°C for a holding time of 12 hours in air atmosphere; thereby a sintered body was obtained.
- Both surfaces of the obtained sintered body were polished using a cylindrical grinder so that the thickness of the obtained sintered body was 4 mm, thereby the target for forming the dielectric film was obtained.
- Next, a square substrate of 10 mm x 10 mm having a SiO2 insulation layer with a thickness of 6 µm on a surface of the Si single crystal substrate with a thickness of 350 µm was prepared. To the surface of this substrate, a Ti thin film having a thickness of 20 nm as an underlayer was formed by a sputtering method.
- Next, on the Ti thin film formed in above, a Pt thin film as the lower electrode having a thickness of 100 nm was formed by a sputtering method.
- To the formed Ti/Pt thin film (the underlayer and the lower electrode), a heat treatment was performed in a temperature rising rate of 400°C/min at a holding temperature of 700°C for a temperature holding time of 0.5 hour under oxygen atmosphere.
- A dielectric film was formed on the Ti/Pt thin film after the heat treatment. In the present examples, the dielectric film was formed by a PLD method so that the thickness was 400 nm on the lower electrode using the target formed in above. A condition for forming the film by a PLD method was oxygen pressure of 1.0 × 10-1 Pa and the substrate was heated to 200°C. Also, in order to expose part of the lower electrode, a metal mask was used to form an area where the dielectric film was not formed.
- Next, an Ag thin film as an upper electrode was formed on the obtained dielectric film using a deposition machine. The upper electrode is formed so as to have a shape having a diameter of 100 µm and a thickness of 100 nm using the metal mask. Thereby, the thin capacitors of Sample No.1 to Sample No.24 having the constitution shown in
FIG.1 were obtained. - Note that, a composition of the dielectric film was analyzed using XRF (X-ray fluorescence element analysis) for all of the samples to confirm that the composition matched the composition shown in Table 1. Also, the thin film capacitor was processed using FIB and the obtained cross section was observed using SIM to measure the length, thereby the thickness of the dielectric film was obtained.
- For all of the obtained thin film capacitor samples, a relative permittivity and a Q value were measured by below described method.
- A relative permittivity and a Q value were calculated (no unit) from the thickness of the above obtained dielectric film and a capacitance which was measured using an RF impedance/material analyzer (4991A made by Agilent) at a standard temperature of 25°C by inputting a frequency of 2 GHz, an input signal level (measuring voltage) of 0.5 Vrms. In the present examples, a relative permittivity of 13.0 or more was considered good which is about 2 times of the relative permittivity of amorphous SiNx film. Also, a Q value of 500 or more was considered good since a Q value of an amorphous SiNx film was about 500. Results are shown in Table 1,
FIG.2A, and FIG.2B .[Table 1] Sample No. (aCa0 + bSr0)-Zr02 Properties a b a+ b Thickness (nm) Q at2GHz (-) Relative perm ittivity at 2GHz (-) Example 1 1 1.51 0.00 1.51 400 502 19.8 2 0.76 0.75 400 505 20.2 3 0.00 1.51 400 510 20.6 4 1.55 0.00 1.55 400 515 19.6 5 0.78 0.77 400 519 20.0 6 0.00 1.55 400 525 20.3 7 2.20 0.00 2.20 400 553 18.3 8 1.10 1.10 400 559 18.6 9 0.00 2.20 400 562 19.1 10 2.60 0.00 2.60 400 559 16.8 11 1.30 1.30 400 562 17.2 12 0.00 2.60 400 567 17.5 13 3.00 0.00 3.00 400 592 15.8 14 1.50 1.50 400 587 16.3 15 0.00 3.00 400 571 16.9 16 4.00 0.00 4.00 400 662 13.5 17 2.00 2.00 400 659 13.7 18 0.00 4.00 400 678 14.3 Com parative example 1 19 1.30 0.00 1.30 400 489 21.2 20 0.65 0.65 400 468 21.5 21 0.00 1.30 400 483 21.8 22 4.50 0.00 4.50 400 709 12.1 23 2.25 2.25 400 699 12.5 24 0.00 4.50 400 693 12.9 - According to Table 1,
FIG.2A, and FIG.2B , when "a + b" was within the above mentioned range in the complex oxide constituting the dielectric film, it was confirmed that the relative permittivity was 13.0 or more and the Q value was 500 or more at 2 GHz. - The thin film capacitor was produced by the same method as Sample No.1 of Example 1 except for forming the dielectric film by a sputtering method, and the same evaluations as Example 1 were carried out. As a target, the same target as the PLD target of Example 1 was used. Results are shown in Table 2.
- The thin film capacitor was produced by the same method as Sample No.1 of Example 1 except for changing the thickness of the dielectric film, and the same evaluations as Example 1 were carried out. Results are shown in Table 2.
[Table 2] Sam ple No. (aCa0+ bSr0)-Zr02 Properties a b a+b Th ickness (nm) 0 at2GHz (-) Relative perm ittiv ity at2GHz (-) Example 1 1 1.51 0.00 1.51 400 502 19.8 Example 2 25 1.51 0.00 1.51 400 514 19.7 Example 3 26 1.51 0.00 1.51 200 505 19.7 27 1.51 0.00 1.51 800 518 19.8 - According to Table 2, when a sputtering method is used as a known method for forming a film (see Sample No.25), it was confirmed that the same properties as Example 1 can be obtained. That is, it was confirmed that the properties of the dielectric composition of the present invention does not depend on the method for forming a film.
- Also, it was confirmed that the same properties can be obtained even when the thickness of the dielectric film was changed. That is, as long as the thickness was within the above mentioned range, it was confirmed that the properties of the dielectric composition of the present invention did not depend on the thickness.
- An electronic component having a dielectric film including a dielectric composition according to the present invention can attain both a high relative permittivity (for example 13.0 or more) and a high Q value (for example 500 or more) even at high frequency bands. Therefore, such electronic component can be suitably used as a high frequency component.
-
- 10
- Thin film capacitor
- 1
- Substrate
- 2
- Underlayer
- 3
- Lower electrode
- 4
- Upper electrode
- 5
- Dielectric film
Claims (4)
- A dielectric deposition film constituted by a dielectric composition including a complex oxide expressed by a general formula (aCaO + bSrO)-ZrO2 as a main component, in which "a" and "b" of the general formula satisfy a ≥ 0, b ≥ 0, and 1.55 ≤ a + b ≤ 4.00, wherein a relative permittivity at 2GHz is 13.0 or more and a Q value is 500 or more.
- The dielectric deposition film according to claim 1, wherein "a" and "b" of the general formula satisfy 1.55 ≤ a + b ≤ 2.20.
- The dielectric deposition film according to claim 1, wherein "a" and "b" of the general formula satisfy 3.00 ≤ a + b ≤ 4.00.
- An electronic component comprising the dielectric deposition film according to any one of claims 1 to 3.
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